CN105237944B - One kind reclaims polyformaldehyde and preparation method thereof with isomerism cross-linking method activeness and quietness - Google Patents
One kind reclaims polyformaldehyde and preparation method thereof with isomerism cross-linking method activeness and quietness Download PDFInfo
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- CN105237944B CN105237944B CN201510764609.0A CN201510764609A CN105237944B CN 105237944 B CN105237944 B CN 105237944B CN 201510764609 A CN201510764609 A CN 201510764609A CN 105237944 B CN105237944 B CN 105237944B
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Abstract
One kind reclaims polyformaldehyde and preparation method thereof with isomerism cross-linking method activeness and quietness, is related to a kind of plastic material and preparation method thereof, and the present invention will reclaim polyformaldehyde forced air drying 6~8 hours under the conditions of 80 DEG C；Dried recovery polyformaldehyde, crosslinking masterbatch, inorganic filler are weighed by weight ratio and puts into 4~6min of high-speed mixer and mixing, and product is produced in extruding pelletization at 220 DEG C -280 DEG C using double screw extruder.Conventional recovery method carries out toughness reinforcing by increasing elastic body toughening agent, it will usually cause the tensile property of polyformaldehyde feed back to decline, so as to influence overall mechanical property；Technical scheme can realize that the effect of polyformaldehyde is reclaimed in enhancing, toughness reinforcing simultaneously, and isomerism cross-linking method be introduced into the regenerative process that can make recovery polyformaldehyde need not add compatilizer can also make regeneration polyformaldehyde toughness and intensity very well, great market popularization value.
Description
Technical field
The present invention relates to a kind of plastic material and preparation method thereof, more particularly to a kind of isomerism cross-linking method strengthens
Toughness reinforcing reclaims polyformaldehyde and preparation method thereof.
Background technology
Polyformaldehyde (English：Polyformaldehyde) also known as acetal resin, the polymer as obtained by oxymethylene polymerization, gathers
It is right not high, and easily by thermal depolymerization.It is the engineering plastics of another high comprehensive performance after polyamide, with high power
Learn performance, such as intensity, modulus, wearability, toughness, fatigue durability and creep resistance, also with excellent electrical insulating property, solvent resistant
Property and machinability, are one of five big general engineering plastics.
The difference of chemical constitution in its strand, can be divided into two kinds of acefal homopolymer and copolymerized methanal.Both important differences
It is：Acefal homopolymer density, crystallinity, fusing point are all high, but heat endurance is poor, processing temperature narrow range（About 10 DEG C）, it is steady to soda acid
It is qualitative lower slightly；And copolymerized methanal density, crystallinity, fusing point, intensity are all relatively low, but heat endurance is good, is not easily decomposed, processing temperature
Scope is wide（About 50 DEG C）, it is preferable to ph stability.
It has good physics, mechanically and chemically performance, especially there is excellent crocking resistance, is the third-largest general plastic
Material.Suitable for making anti-attrition wear part, driving parts, and chemical industry, the part such as instrument.The compliance of polyformaldehyde strand is big,
The structural regularity of chain is high, thus crystallinity is high, and crystallizing power is strong.The crystallinity of acefal homopolymer is 75%-85%, and copolymerized methanal is
70%-75 %, even if rapid quenching, crystallinity can also reach more than 65%.The polyformaldehyde of completely amorphous state is only at -100 DEG C
It can just obtain.High density and high-crystallinity are the main causes that polyformaldehyde has premium properties, and such as hardness is big and modulus is high, size
Stability is good, and fatigue durability is protruded, and is difficult to be corroded by chemical mediator.
In recent years, with the demand of industrial development, concern of the people to the study on the modification of polyformaldehyde also all the more.Polyformaldehyde
(POM) with the cost less than other many engineering plastics, some markets traditionally captured by metal are being substituted, are such as being substituted
Zinc, brass, aluminium and steel make many parts, and since the advent of the world, POM has been widely used for electric, mechanical, instrument, day
With fields such as light industry, automobile, building materials, agriculturals.In terms of the application of many frontiers, such as medical technology, sports apparatus, POM
Also preferable growing trend is shown.But it is corroded by strong acid, weather resisteant is poor, poor adhesion, and thermal decomposition is approached with softening temperature,
Limited oxygen index is small, therefore research need to be modified to it.
The content of the invention
It is an object of the invention to provide one kind polyformaldehyde and its preparation side are reclaimed with isomerism cross-linking method activeness and quietness
Method, the present invention realizes enhanced effect while toughness reinforcing, solves because causing asking for tensile strength decline using elastic body toughening
Topic, and being introduced into the regenerative process that can make recovery polyformaldehyde for isomerism cross-linking method need not add compatilizer and can also make
Regeneration polyformaldehyde has preferable overall mechanical properties, so as to reuse, great market popularization value.
The purpose of the present invention is achieved through the following technical solutions：
Polyformaldehyde is reclaimed with isomerism cross-linking method activeness and quietness, based on mass weight part, is included：Reclaim polyformaldehyde
60~80 parts；10~30 parts of toughener；10~30 parts of crosslinking masterbatch；5~10 parts of inorganic filler.
Described use isomerism cross-linking method activeness and quietness reclaims polyformaldehyde, and the toughener is POM/POE, POM/EVA
At least one of.
Described use isomerism cross-linking method activeness and quietness reclaims polyformaldehyde, and described crosslinking masterbatch are by A material B material and produced
Aqua is constituted：
A expects composition:Acetal resin
Silane crosslinker（Vinyltrimethoxy silane）
Initiator（Cumyl peroxide (DCP)）
B expects composition：Acetal resin
Catalyst（Dibutyl tin laurate）
Antioxidant（Antioxidant 1010）
Produce aqua composition：Acid and metal oxide.
Described use isomerism cross-linking method activeness and quietness reclaims polyformaldehyde, it is characterised in that：Acid in the production aqua
For at least one of stearic acid, inorganic acid.
Described use isomerism cross-linking method activeness and quietness reclaims polyformaldehyde, it is characterised in that：Gold in the production aqua
Category oxide is at least one of zinc oxide, tin oxide.
Described use isomerism cross-linking method activeness and quietness reclaims polyformaldehyde, it is characterised in that：The filler be calcium carbonate,
At least one of talcum powder.
Polyformaldehyde preparation method is reclaimed with isomerism cross-linking method activeness and quietness, methods described includes following preparation process：
A, 95 parts of A material are weighed by mass fraction, be put into extruding pelletization in double screw extruder after 4.5 parts of B material mixing, then
Again with 0.5 part of production aqua（Stearic acid and zinc oxide 1:1 mixture）It is well mixed to be put into double screw extruder extruding pelletization shape
Into crosslinking masterbatch；
B, by weight ratio by crosslinking masterbatch, reclaim polyformaldehyde, inorganic filler and put into high-speed mixer high speed and mix 4
~6 minutes, it is set uniformly to mix；
C, the material being well mixed in above-mentioned high-speed mixer is added in double screw extruder hopper to carry out melting mixed
Refining, extruding pelletization obtain regenerating polyformaldehyde.
Described use isomerism cross-linking method activeness and quietness reclaims polyformaldehyde preparation method, the spiral shell of the double screw extruder
Bar temperature control is between 220 DEG C -280 DEG C.
Advantages of the present invention is with effect：
The present invention is crosslinked law technology by isomerism, and enhanced effect can be realized while toughness reinforcing, solves because making
Cause the problem of tensile strength declines with elastic body toughening, and the introducing of isomerism cross-linking method can make recovery polyformaldehyde
Compatilizer need not be added in regenerative process can also make regeneration polyformaldehyde have preferable overall mechanical properties, so as to again
It is secondary to use, great market popularization value.
Embodiment
With reference to specific embodiment, the present invention is described further：
The weight distribution ratio of each component is as shown in table 1 in embodiment 1-3, each embodiment.Each component is weighed by proportioning,
Mixed 5 minutes in homogenizer, the raw material of compound is placed in double screw extruder and makes material by discharging, the temperature of extruder
Degree is in 220 DEG C -280 DEG C, rotating speed 150r/min.Batten is prepared, by corresponding standard testing（It is shown in Table 2）Results of property is shown in Table 3.
Table 1：Embodiment 1-3 and the formula of comparative example 1 composition (part）
Table 2：Mechanics Performance Testing standard
| Test event | Testing standard |
| Tensile strength MPa | GB/T 1040.1-2006 |
| Elongation at break % | GB/T 1040.1-2006 |
| Bending strength MPa | ASTM D-790 |
| Bending modulus MPa | ASTM D-790 |
| The strong KJ/m of notch shock2 | GB/T 1043-93 |
Table 3：The Mechanics Performance Testing of polyformaldehyde is regenerated in embodiment 1-3
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Tensile strength MPa | 60 | 65 | 60 | 70 |
| Elongation at break % | 9% | 11% | 13% | 15% |
| Bending strength MPa | 80 | 85 | 90 | 85 |
| Bending modulus MPa | 2500 | 2400 | 2700 | 2600 |
| The strong KJ/m of notch shock2 | 3 | 4 | 5 | 7 |
From the embodiment 1-3 of table 3 and the mechanical experimental results of comparative example 1, we understand：Using toughener merely
When, the tensile property of material can be reduced while reclaiming polyformaldehyde impact property by improving；After isomerism cross-linking method,
The tensile property for reclaiming polyformaldehyde can also be improved while being improved with crosslinking masterbatch and reclaimed polyformaldehyde impact property；And homogeneity
Being introduced into the regenerative process that can make recovery polyformaldehyde of isomery cross-linking method, which need not add compatilizer, can also make regeneration polyformaldehyde
Toughness and intensity it is fine；Isomerism cross-linking method does not influence substantially on the bending strength and bending modulus that reclaim polyformaldehyde.
Claims (7)
1. reclaim polyformaldehyde with isomerism cross-linking method activeness and quietness, it is characterised in that based on mass weight part, include：Return
60~80 parts of pinching formaldehyde；10~30 parts of toughener；10~30 parts of crosslinking masterbatch；5~10 parts of inorganic filler；
Described crosslinking masterbatch are made up of A material B material and production aqua：
A expects composition:Acetal resin
Silane crosslinker is vinyltrimethoxy silane
Initiator is cumyl peroxide DCP
B expects composition：Acetal resin
Catalyst is dibutyl tin laurate
Antioxidant is antioxidant 1010
Produce aqua composition：Acid and metal oxide.
2. use isomerism cross-linking method activeness and quietness according to claim 1 reclaims polyformaldehyde, it is characterised in that：It is described to increase
Tough dose is at least one of POM/POE, POM/EVA.
3. use isomerism cross-linking method activeness and quietness according to claim 1 reclaims polyformaldehyde, it is characterised in that：The production
Acid in aqua is at least one of stearic acid, inorganic acid.
4. use isomerism cross-linking method activeness and quietness according to claim 1 reclaims polyformaldehyde, it is characterised in that：The production
Metal oxide in aqua is at least one of zinc oxide, tin oxide.
5. use isomerism cross-linking method activeness and quietness according to claim 1 reclaims polyformaldehyde, it is characterised in that：The nothing
Machine filler is at least one of calcium carbonate, talcum powder.
6. reclaim polyformaldehyde preparation method with isomerism cross-linking method activeness and quietness, it is characterised in that methods described includes following
Preparation process：
A, 95 parts of A material are weighed by mass fraction, extruding pelletization in double screw extruder, Ran Houzai are put into after 4.5 parts of B material mixing
It is well mixed with 0.5 part of production aqua and is put into double screw extruder extruding pelletization formation crosslinking masterbatch；
B, by weight ratio by crosslinking masterbatch, reclaim polyformaldehyde, inorganic filler put into high-speed mixer high speed mix 4~
6 minutes, it is set uniformly to mix；Described production aqua is stearic acid and zinc oxide 1:1 mixture；
C, by above-mentioned high-speed mixer be well mixed material be added in double screw extruder hopper carry out melting mixing, squeeze
Go out granulation to obtain regenerating polyformaldehyde；
The A expects composition:Acetal resin
Silane crosslinker is vinyltrimethoxy silane
Initiator is cumyl peroxide DCP
B expects composition：Acetal resin
Catalyst is dibutyl tin laurate
Antioxidant is antioxidant 1010.
7. use isomerism cross-linking method activeness and quietness according to claim 6 reclaims polyformaldehyde preparation method, its feature exists
In：The extruder temperature of the double screw extruder is controlled between 220 DEG C -280 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510764609.0A CN105237944B (en) | 2015-11-10 | 2015-11-10 | One kind reclaims polyformaldehyde and preparation method thereof with isomerism cross-linking method activeness and quietness |
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| JPS5582127A (en) * | 1978-12-19 | 1980-06-20 | Hitachi Cable Ltd | Method of crosslinking polyolefin and preparation of electric wire insulated with crosslinked polyolefin |
| NL7908964A (en) * | 1979-12-13 | 1981-07-16 | Akzo Nv | PROCESS FOR PREPARING MASTERBATCHES OF PEROXIDES IN POLYMERS. |
| CN101173081A (en) * | 2006-10-31 | 2008-05-07 | 佛山市顺德区汉达精密电子科技有限公司 | Polyoxymethylene modified material |
| CN102617907A (en) * | 2012-03-02 | 2012-08-01 | 浙江宝利纳材料科技有限公司 | Recycled high-density polyethylene modified material containing polypropylene and modifying method thereof |
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